Patent GB-523396-A (GB)
Title: Manufacture and application of ether and ester condensation products
IPC: C07D213/20
Filed: 1938-11-03
Abstract: 523,396. Waterproofing fabrics. SOC. OF CHEMICAL INDUSTRY IN BASLE. Nov. 3, 1938, Nos. 31845, 31846, 31847 and 31848. Convention dates, Nov. 5, 1937, Jan. 4, 1938, Feb. 3, 1938 and Oct. 14, 1938. Samples furnished. [Class 140] [Also in Groups IV and III] A halogen methyl compound having the formula R 1 XCH 2 -halogen, wherein R, is any organic residue and X is O, S or COO is condensed with a compound having the formula R 2 YH wherein R 2  is any organic residue and Y is O or COO. When the starting materials and products do not contain a water solubilising group viz.: a sulphonic, sulphuric acid ester or thiosulphuric acid ester group, an onium group or an amino, imino or residue containing an amino or imino group (in salt form), a halogen atom or a hydroxy group must be present and the halogen atom is replaced by a thiosulphuric acid ester group, an onium group, an amino, imino or residue containing an amino or imino group (in salt form), or the hydroxy group is sulphonated in order to render the product water soluble. The water solubilizing group is so situated in the molecule that there are at least two carbon atoms between the water solubilizing group and the oxygen or sulphur of the nearest group X or Y. In examples: (1) potassium chloracetate is condensed with a mixture of α- chlormethylethers derived from a mixture of octa- and hexa-decyl alcohols and a pyridinium compound is formed by treating with pyridine. A solution of the product which may also contain sodium acetate may be used for treating textiles, e.g., cotton, which is thereby rendered soft and water repellent; the product also prevents bleed- . ing of cotton dyed with direct-fast-violet 2RL and improves the affinity of cellulose or cellulose hydrate for direct and acid dyestuffs: (2) the ester of chloracetic acid prepared in the previous example is rendered water soluble by treating with sodium thiosulphate: (3) potassium chloracetate is condensed with stearic acid chlormethyl ester and the resulting ester after extraction with acetone reacted with pyridine: (4) the chlorester prepared in the previous example is rendered water soluble by treating with thiourea in glacial acetic acid: (5) chlormethyl-#-chlormethyl ether is condensed with a mixture of octa- and hexa-decyl alcohols and the product converted into pyridinium compounds. The products, when they contain an aliphatic or cycloaliphatic residue of high molecular weight have wetting, emulsifying, foaming and levelling properties. They form salts which are decomposed by heating or saponifying, insoluble products being formed. By decomposing the salts on textiles the latter are rendered waterproof. Intermediates may similarly be deposited upon textiles and then converted into dyestuffs. The products may be used in association with sodium acetate or other salt, solvents, soap, colloids and loading, softening and wetting agents. The following α-halogenmethyl carboxylic acid esters, ethers and thioethers may be used as starting materials:- α-chlormethyl esters of lauric, chloracetic, α-bromlauric and sulphoacetic acids, α-halogen methylethers derived from aliphatic, cycloaliphatic and aliphatic-aromatic alcohols and phenols such as amyl, octyl, cetyl, oleyl and benzyl alcohol, methylcyclohexanol, alkylated phenols, glycerol mono- and diethers and alkanolamines acylated at the nitrogen by fatty acid residues, ethylenechlorhydrin-α-chlormethylether, chlorethoxyethylpyridinium chloride, the α-chlormethylether obtained from hydroxyethanesulphonic acid, hydrochloric acid and formaldehyde and α-halogenmethyl sulphides obtainable from lauryl, octadecyl or #-chlorethylmercaptan, hydrochloric acid and formaldehyde. For reacting with the α-halogenmethyl compounds carboxylic acids of the aliphatic, cycloaliphatic or aromatic series may be used such as undecylenic, palmitic, resinic, dichloracetic, chlormethylbenzoic, chlormethylsalicylic, glycollic, lactic, 4-dialkylamino-1-benzoic, sulphoacetic, sulphochloracetic, sulphosuccinic, 4-sulphophthalic and 3-sulphonaphthalic acid, and the alcohols mentioned include amyl, myristyl, cetyl, benzyl, resin and naphthenic alcohols, glycol, polyglycols, glycerol, polyglycerols, mannitol, mono - and poly - saccharides, hydoxethylpy - ridinium chloride, hydroxyethane sulphonic acid and ethylenechlorhydrin. - A sample has been furnished under Sect. 2 (5) of a product obtained by condensing sterol with chlormethylchlorethylether and treating the product with a suspension of thiourea in acetone. The Specification as open to inspection under Sect. 91, comprises also the condensation of compounds having the formula R 1 XCH 2 OT or any functional derivative thereof wherein R<SP>1</SP> is an organic residue and X is O, COO, S, NR<SP>3</SP> or an amide-like residue, R<SP>3</SP> is hydrogen or a hydrocarbon residue with compounds having the formula HYR 2  wherein R, is an organic residue and Y is O, COO, S, NR 3 , or an amide-like residue, the product having a water solubilising group in such a position that there are at least two carbon atoms between the atom or group X or Y and the said water solubilising group. Either X or Y must be oxygen or a COO group. Water solubilising groups include the phosphoric ester, phosphonium and sulphonium groups. Additional examples include: (1) lauric and stearic acid methylol amides are condensed in pyridine with benzoic acid sulphochloride; fabrics may be rendered water repellent by impregnating them with a solution containing the product and formic acid or sodium carbonate and heating the fabric after squeezing and drying ; salts, e.g., aluminium formate or magnesium sulphate may be added to the treating liquor; fabric dyed with acid, mordant, vat, direct sulphur or pigment dyes are rendered fast to light and washing. (2) benzoic acid sulphochloride is similarly condensed with a solution of abietic or stearic acid amide in pyridine to which paraformaldehyde has been added: (3) stearic acid chloride is reacted with N-methylolchloracetamide in pyridine: (4) stearic acid N-methylamide is condensed with chlormethyl-#-chlorethylether and pyridine added to the product: (5) laurylmercaptan is condensed with chlormethyl-#-chlorethylether and pyridine added to the product: (6) esters derived from thioglycollic acid and a mixture of octa-acid hexa-decyl alcohols are condensed with chlormethyl-#-chlorethylether and the resulting mixture reacted with pyridine: (7) lauric acidmethylolamide is condensed with p-chlormethylbenzoylchloride in the presence of pyridine. Methylolamides which may be used as starting materials include methylolamides of chlor or brom acetic acid and of α-bromlauric acid, N- methylolsulphoacetamide and N-methylolsulphobenzamide. The oxymethylthioether derived from thioglycollic acid amide is mentioned as an example of a methylol compound of a mercaptan and thioglycollic acid esters and amides, e.g., thioglycollic acid anilide, monothioglycerol and mercaptoethanesulphonic acid are mentioned as second components containing sulphur. Amines derived from resin and naphthenic acids, methyloctadecylamine, N-hexadecylaniline and naphthylamines are examples of components containing nitrogen. Stearic acid-N-methylamide and stearic acid -o-toluidide may also be used. This subject-matter does not appear in the Specification as accepted.